JPS60149535A - Alcohol continuous manufacture - Google Patents

Abstract

A process for producing a lower aliphatic alcohol by splitting ethers whereby ethers are reacted at an elevated temperature and pressure with an excess of water in the presence of acidic hydration catalysts is disclosed.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to ethers and ether mixtures having the general formula % (wherein R and R1 are alkyl groups each having 1 to 5 carbon atoms) This invention relates to a continuous process for producing alcohol by decomposing it under high temperature and pressure in the presence of an acidic catalyst.

[Prior art]

The decomposition reaction of ethers is usually carried out to obtain pure olefins. In the related patents of Ofuyu, the ether is first obtained from an olefin-containing mixture containing alcohol in the presence of an ion exchange resin, and then this reaction is carried out to obtain pure olefins. The ether is decomposed at high temperatures in the presence of an acidic catalyst, thereby yielding pure olefins and alcohols.

For example, in DE 2,802,199 and EP 6,605, pure isobutyne is obtained by this method from a C4 hydrocarbon stream using a C3'-C4 alcohol, and each In this case, the 6th butyl ether is produced as an intermediate.

During the synthesis of alcohols by acidic watering of olefins, ethers are formed as undesirable by-products. It is known that this ether formation can be reduced by recycling the ether distilled off from the alcohol.

U.S. Pat. No. 2,050,445 describes a process for the continuous production of phosphoric acid using an aqueous solution of phosphoric acid as a catalyst and recycling diethyl ether together with the recycle gas. It has been reported that by doing so, the production of ether can be further suppressed (page 5, left column, lines 44-54).

On the other hand, Canadian Patent No. 867.797 describes that diisopropyl ether is recycled as a circulating gas during the synthesis of inpropyl alcohol from propylene. In order to increase the yield of ethanol and isopropanol during their synthesis, it has already been carried out to recirculate the produced ether reed as a recycle gas.

DE 2,759,237 describes recycling the formed by-products to the feedstock before entering the reactor.

[Problem that the invention seeks to solve]

However, an additional difficulty arises when attempting to completely suppress ether production by recycling ether into the feedstock fed to the reactor.

Specifically, tests have shown, for example, in the synthesis of isopropyl alcohol, that space/time yields are reduced by as much as 60% to 50%, depending on the concentration of the propylene feedstock. Furthermore, if large amounts of gas are recycled, ie, the gas conversion per pass is low, then a significant amount of ether must be recycled. More energy is consumed to evaporate the ether in the feedstock.

There is a method for decomposing the ether by passing the gaseous ether over alumina.

Met
Organischen Che
mie) Vi 5 (1965-), p. 146. However, in this case, the reaction of diisopropyl ether yields propane and a very small amount of alcohol.

Now, there is no known method for the direct conversion of aliphatic ethers according to the formula % (%) (where R and R' each represent an alkyl group having 1 to 5 carbon atoms).

[Means for solving problems]

The object of the invention is to provide a process for the preparation of the corresponding alcohol or alcohol mixture by direct, quantitative conversion of the ether.

In the present invention, an ether represented by the general formula % (in the formula, R and R each have 1 to 5 carbon atoms and represent an alkyl group) is heated at a temperature of 100 to 180° C.
Contact with excess water in the presence of a conventional acidic water conservancy catalyst under a pressure of 0 to 100 bar, recycling the liquid ether phase and withdrawing the aqueous phase containing the alcohol produced from the reactor. Aqueous phase known method scales.

We are trying to solve this problem by using a production method that is characterized by recovery.

In a preferred embodiment of the process of the invention, the alcohol contained in the liquid ether phase is preferably extracted from the liquid ether phase, especially with water, prior to recycling the ether phase to the reactor. [Operation] According to the production method of the present invention, direct quantitative conversion of ether to alcohol can be performed. In particular, only the aqueous phase containing the alcohol produced needs to be withdrawn from the production process. The alcohol (which also contains small amounts of dissolved ether) is then distilled off from the alcoholic solution by known methods.

Surprisingly, according to the production method of the present invention, virtually no olefin is produced. Gas is also not exhausted from the reaction system. During the decomposition of inglovir ether, propylene with an FC of 2 to 6% is dissolved in the organic phase, and at this level, propylene is in an equilibrium state.◇The polypropylene contained is not separated and is continuously transferred to the reactor together with the ether. Recirculate.

A specific example of the manufacturing method of the present invention will be explained with reference to the accompanying drawings.

Referring to FIG. 1, ether from tube 1 and water from v3 are continuously introduced together through tube 4 into a tubular reactor 6 filled with ion exchange resin. Ethers are hydrolyzed by acid-catalyzed multiphase reactions at high temperatures and pressures. The alcohol and two educts formed spread into two immiscible liquid phases: the alcohol/water phase and the ether/alcohol phase.

Alcohols are advantageous in this step because they dissolve more quickly in the aqueous phase than ethers. After the two phases have separated, the desired reaction product and a small portion of ether are drawn off through line 5 together with excess water. Unreacted ether and a small amount of olefin are separated in the upper part of the reactor as an upper layer, which is recycled via line 7 to busy reactor 6 without any intermediate treatment. The lighter phase (ether/alcohol), which is separated at the top of the reactor to decompose a large amount of ether (over 90%) and ensure thorough mixing of the two phases, reacts at a relatively high rate. Recirculate into the liquid phase of the vessel.

In this way, the recycled olefin can also be hydrated to alcohol under reaction 4, so that the ether feed can be completely converted to alcohol. (This excludes the ether withdrawn with the aqueous phase containing the product, which also, after distillation,
Can be recirculated. ) If we do not include recycling of the ether phase-separated with the alcohol, the conversion is ν0
~96chi. And if you also include recirculation, what about shavings?
'ii' A conversion rate of 100 degrees can be achieved.

In FIG. 2, the recirculated flow passes through line 8 to extractor 94C.
The alcohol contained in the recycle stream is extracted with water supplied via line 10 and recovered via line 11 at a lower temperature of 80-100°C. The alcohol-free recycle stream is then reheated in '1iF12 and recycled to the cracking reactor.

The catalyst for decomposing ether is usually a liquid or solid catalyst used for the utilization of water from olefins, and solid catalysts are particularly preferred. Temperature-stable ion exchange resins of the sulfonic acid type are particularly preferred.

The temperature in the decomposition reactor is preferably in the range of 100 to 180°C. When using an organic ion exchange resin, the upper temperature limit is determined by the heat resistance of the catalyst. The pressure is 10-1
The method for decomposing ether is highly pressure dependent. The pressure is such that the two phases can remain liquid.

In the ether decomposition method of the present invention, the ether/water molar ratio is
It is necessary to use approximately 1 mole of ether to 3 moles of water. Further, it is preferable that the molar ratio is about 1 mole of ether to water with a molar ratio of 10 moles, particularly preferably 50 to 50.
For a molar ratio of about 1 mole of 9 ether to 100 moles of water, the space/time yield is 1 to 2 moles of alcohol per catalyst time, and the recycle stream is If the extraction does not contain alcohol, 6.5 mol/
The alcohol content in the aqueous phase of stream 5 in the decomposition of diisopropyl ether is between 10 and 15 i1f, and the ether content in the aqueous phase is at most about 1 wt. is usually no more than this.

〔Example〕

The following examples serve to further explain the invention with the help of FIGS. 1 and 2. In the following, "beruchi" means "abusive word".

Example 1 Am, a strongly acidic ion exchange resin used as a catalyst
Inner size 26a filled with 2.5z berlite 252
In a reactor 6 (according to FIG. 1) with a length of 5 m and a tube 1
Inglovir ether was introduced through the tube at 254 f/hr, and deionized water was introduced through line 6 at 2225 r/hr. 26 t/h of the upper organic layer produced in the reactor, consisting of 72 g undecomposed ether, 20 q/b isopropyl alcohol, 5% water and 6% propylene, is reacted with the ether feed through line 7. It was recirculated to the water reservoir of vessel 6. Using a heating jacket, the temperature inside the reactor was adjusted to 155°C. The pressure inside the reactor was increased to 50
kept in a crowbar.

From reactor 6, an aqueous liquid phase containing 11.0% isopropyl alcohol and 1% diisopropyl ether was withdrawn through line 5 at 2455 r/h. Isopropyl alcohol was produced in 1089 (1.8 mol)/catalyst hour. No gas phase formed.

Example 2 The procedure described in Example 1 was repeated except that the reaction pressure was 25 bar. Results similar to those in Example 1 were obtained.

Example 6 Using the apparatus shown in FIG. 2, the upper organic phase is cooled to 100° C. using heat exchanger 15 before being introduced into extractor 9 through tube 8 and recycled ether. The same procedure as in Example 1 was repeated except that the isopropyl alcohol portion was removed from the sample. Thus, the ether feed charged through tube 1 resulted in 5.9 liters of isopropyl alcohol at 3440 F from tube 5, still containing 0.5% i-thyl. Another 256,197 hours of isopropyl alcohol water bath solution was obtained through tube 11. The isopropyl alcohol content in this aqueous phase averages 11.
At 9%, the isopropyl ether content was 0.9 yen.

Isopropyl alcohol iE, 1941 (5,2 mol)
/ was obtained in catalytic time.

Example 4 The procedure of Example 6 was repeated except that 495° of di-sec-butyl ether was fed through line 1 and 65,989 deionized water was fed through line 6. Also, 648,417 hours of 648,417 hours of 6.2 hours of di-butyl alcohol were obtained from tube 5, which still contained 0.04% di-butyl ether with 69,669 hours of water placed in extractor 9. 0, 0 again
7400 f/hr of 6% sec-butyl alcohol containing 6% di-sec-butyl ether was obtained from tube 11. The stream recycled to reactor 6 via line 12 contains 88% di-sec-butyl ether, 2-6% butene,
It contained about 9 ml of sec-butyl alcohol and 1,000 ml of water.

222r (3.0 mol) of sec-butyl alcohol were obtained in catalytic time.

[Brief explanation of drawings]

FIG. 1 is a simplified block diagram of the catalytic reaction apparatus, and FIG. 2 is a block diagram in which an extractor for separating the produced alcohol from the recovered organic layer is combined. DESCRIPTION OF SYMBOLS 1... Raw material ether supply line, 2... Water supply line, 5... Produced alcohol extraction line, 6... Reactor, 7... Recirculation line, 9... Extractor, 10...・
・Extract water supply line, 11...extract liquid take-out line,
16... Heat exchanger. Agent Patent Attorney Sanro Kimura

Claims (1)

[Claims] , C11 General formula % Formula % (R and R1 are each an alkyl group containing 1 to 5 carbon atoms.) ' An ether represented by the formula % is heated in the presence of an acidic catalyst. When reacting at high pressure to produce lower aliphatic alcohols having 1 to 5 carbon atoms, ether is mixed with excess water and 100 to 18
A liquid ether phase consisting of ether and alcohol is mixed with water in the presence of an acid water conserving catalyst at a temperature of 0° C. and a pressure of 10 to 100 bar, sufficient to keep the two starting components in the liquid phase. and alcohol, recycling the liquid ether phase to the reactor, withdrawing from the reactor the aqueous phase containing the produced alcohol, and recovering the aliphatic alcohol from the aqueous phase. continuous manufacturing method. (21) Process according to claim 1, in which the aliphatic alcohol contained in the liquid ether phase is extracted with water before recycling the ether phase to the reactor.